CN1507466B

Movatterモバイル変換

Info

Publication number: CN1507466B
Application number: CN028094794A
Authority: CN
Inventors: 弗烈德·谢芬林·比勒
Original assignee: EMS Chemie AG
Current assignee: EMS Chemie AG
Priority date: 2001-05-08
Filing date: 2002-04-18
Publication date: 2012-06-20
Anticipated expiration: 2022-04-18
Also published as: BR0209140A; TW583255B; CN1507466A; DE50214146D1; AU2002319141A1; JP2004532321A; DE10122188A1; WO2002090421A3; EP1397414A2; US20040158028A1; CA2446508C; DE10122188B4; CA2446508A1; US7053169B2; JP4262987B2; ATE454416T1; HK1059628A1; EP1397414B2; WO2002090421A2; EP1397414B1

Abstract

The invention relates to novel thermoplastic, transparent copolyamide-based polyamide moulding compounds, containing diamines and dicarboxylic acids with aromatic nuclei, said compounds having a high refractive index > 1.60 with a low density, less than 1.3 g/cm<3>. Said materials also exhibit a low birefrigence, a high degree of hardness and scratch resistance. They are produced on conventional pressure autoclaves, according to a modified method. The inventive moulding compounds are shaped using thermoplastic processes and in relation to known substances such as PMMA or PC, they unite optically significant characteristics such as a high refractive index, degree of hardness and a high thermal stability in one product. In addition to the favourable combination of characteristics, moulded parts produced from the inventive moulding compounds exhibit the excellent chemical resistance inherent to polyamides. It is desirable for optical lenses to have an extremely low birefringence to prevent the formation of colour rings or distortion.

Description

Be used to prepare the polyamide molding compounds of optical lens

Technical field

The invention relates to a kind of transparent polyamide moulding material of handling based on the novel thermoplastic of copolyamide, RI n_D²⁰Surpass 1.59, preferably surpass 1.6, and viscosity is at 1.3g/cm³, comprise diamines and dicarboxylic acid copolymers.Simultaneously, obtained low double refraction, the performance of high firmness and scrape resistant.

Polyamide molding material of the present invention is according to improved technology, prepares through conventional pressure reactor drum (autoclave).With moulding material of the present invention through such as injection-molded, especially the thermoplastic method in the multi-cavity instrument forms and obtains particle.

The present invention is also about the use in the preparation optical lens based on the moulding material of the present invention of specific copolyamide.

Background technology

Term " transparent polyamide " refers to (being total to) polymeric amide (for example moulding material) here, when the thickness of polymeric amide is the form of thin lens of 2mm, and its transmission factor at least 70%.

Mainly through the preparation of highly shrinkable moulding resin, this resin is cured through UV activatory solidifying agent in mould the optical lens moulding mixture.Usually curing can reduce volume 20% or more.Complicated geometrical shape is no longer separated mould (demold).An advantage of this method is that moulding resin can be loaded into and can obtains RI n_D²⁰Greater than 1.60 with the compound of high hardness and heat-drawn wire in.Protect the hardness protecting materials and prevent surface disturbance.Main drawback is long set time, reaches 40 hours, and the composition of pouring the relative complex in high-purity mould into.

The manufacturing speed of the optical lens of moulding according to injection moulding process improves manyfold.Compare with reactive moulding resin, handle simpler.Can obtain high complicated how much.The back injection molding technology that use is known can be made the compsn that has other polymeric amide.What at present, be used for lens mainly is the amorphous plastics such as PMMA polymethyl acrylate or PV (gathering carbonic acid).The advantage of PMMA is low treatment temp, high transparent and high firmness.Its insufficient place is low heat-drawn wire and 1.49 low RI n_D²⁰The advantage of PC is good viscosity and mean refractive index n_D²⁰Be 1.59.On the other hand, its shortcoming is low hardness and low chemical resistant properties.

PS (PS) or COC (cyclic olefine copolymer) with high heat-drawn wire are other amorphous plasticses, are suitable for making lens.Their RI n_D²⁰With gather the about the same of carbonic acid.Its insufficient place is low hardness, low heat-drawn wire and low chemical resistant properties.

In order to obtain high RI n_D²⁰With low dispersion, the appropriate addn with high electron density and high polarization ability joins in the molding compounds of use.Generally speaking, the heavy atom of the for example iodine in suitable compound or salt can use.Perhaps, can use surface grinding, improve such as RI n_D²⁰, dispersion, transmission and hardness etc. performance.

Usually, in being suitable for preparing the pressure autoclave of polymeric amide, make thermoplasticity, semi-crystalline and the opaque polyamide molding compounds that contains fat or aromatic dicarboxilic acid and aliphatic diamine.In these methods, temperature is between 250-350 ℃, and pressure is between 10-20bar.After having reacted, with polymer melted, the shape that nozzle forms line is crossed in conducting, in water-bath, cools off, and is cut into particulate state.Then that these particle refuses are profile extruded again or be injection molded into product in forcing machine.

Make to use the same method, use monomer just can make transparent thermoplastic polyamide molding compounds.Wherein, crystal constitutes by monomer inhibition altogether.Product with high aromatic content contains high glass transition temp and HV and can not be again because low flowability emit usually from autoclave.In order to increase flowability, aliphatics is total to monomer links together, reduce glass transition temp.

Yet, use the method for autoclave and prepare RI n with the method for injection-molded system_D²⁰Surpass 1.6, density is at 1.3g/cm³Below, high firmness and low glass transition temp are used for the also not known road of thermoplastic transparent polyamide molding material that the official learns use.

Use 2, the phenylbenzene radical that 2-is substituted, be suitable for preparing film and optical fiber, describe to some extent at US-A-4843141 according to a kind of thermoplastic poly ammonia of the autoclave processes preparation of having known.The anisotropy fused formation that reaches 350 ℃ is the characteristic an of necessity.In US-A-4355132, under two kinds of situation, can both obtain 400 ℃ anisotropy fusion, during the liquid crystal characteristic is described in the above.

US-A-4446305 has described a kind of RI n that is used for_D²⁰It is 2.0 transparent polyamide mould.Purpose is to make to have birefringent opaque products.In solution; Normally similar with US-A-4520189 with US-A-4384107 N-methyl pyrrolidone solution under the low temperature in trial stretch, is made; Wherein preferably use aromatic reactant property muriate, though this muriate at room temperature also can with diamine reactant.Its weak point is that solvent has to be removed, and removing of HCL is a very complicated washing process.Need to confirm high index n_D²⁰Specific dicarboxylicacid or diamines do not have enough stability usually so that in autoclave 200-300 ℃ of following melting and solidification.

Can know from US-A-4216321 greater than 235 ℃ various opaque products based on various polyimide and polyetherimide, Tg, and in solvent, under the low temperature, make and injection moulding again that purpose is to prevent thermal damage and decolouring.

US-A-5049156 has described a kind of imido transparent polyamide that is used for lens, and it is with the preparation of fragrant terephthalic acid and aromatic diamines, in organic solvent, changes into amino acid under 80 ℃.When solvent is filtering under vacuum, produce closing of ring, generate imide whereby.Prepare the respective molded body with solvent., and injection moulding and the curing again under heated pressure, under the 200-400 ℃ of grace lattice.The RI n that produces_D²⁰Be 1.6-1.7.

EP-A-556646 has described a kind of reactive epoxy mold resin with xylylene amine compound, uses this resin to be used to prepare moulding RI n_D²⁰Be 1.58 lens.

GB-A-1420741 described a kind ofly have trimethylcyclohexyl diamines and terephthalic acid carboxylic acid, than the amount of refraction height of PMMA but RI n_D²⁰Water type contact lens at the transparent thermoplastic polyamide molding thing below 1.59.

JP09012716 and JP09012712 have described a kind of transparent polyamide thermoplastic, use dimerization or three polyglycerol fatty acids or have the diamines of 11-22 carbon atom and method that ethylene diamine gathers through carboxylic obtains.The transparent lens density that injection moulding produces is 0.957, light transmission 91.2%, relative low-refraction 1.496.

EP-A-619336 has described a kind of transparent thermoplastic polyamide molding compounds, is to carry out polycondensation through the another kind of diamines that right-(4-aminocyclohexyl) methane and usefulness 12 (alkane) dicarboxylicacid that reaches 65% are transformed to obtain.The injection moulding transparent lens demonstrates lower RI n_D²⁰, for example be approximately 1.51.

EP-A-837087 has described a kind of transparent thermoplastic polyamide molding compounds, be through to can be 50% substituted by aromatic carboxylic acid, have a C₈-C₁₄The cycloaliphatic acids C of dicarboxylicacid₁₄-C₂₂Diamines perhaps has cycloaliphatic C₇-C₃₆The fatty C of dicarboxylicacid₈-C₁₄Form.Injection moulding transparent lens density is 1.01g/cm³, RI n_D²⁰Be 1.51 with the Abbe coefficient be 52.

JP-A-3050264 described (A) through such as to the cyclohexyl diamines of (4-amino-3-methylcyclohexyl) methane or right-(4-amino-3-methylcyclohexyl) propane or carboxylic acid diamines and such as the aromatic dicarboxilic acid of isophthalic acid or terephthalic acid with (B) such as PA66 (polyamide 66) PA66; PA6, the transparent thermoplastic polyamide molding compounds that the carboxylic acid polymeric amide of PA11 forms.Can obtain RI n_D²⁰Be below 1.59.

JP-A-3033157 has described a kind of mixture; Comprise: (A) 90% transparent thermoplastic polyamide molding compounds; This compound is perhaps to form such as the aromatic dicarboxilic acid of isophthalic acid or terephthalic acid through cyclohexyl diamines or alicyclic diamine such as right-(amino-3 methylcyclohexyls of 4-) methane or propane; (B) 10% semi-aromatic polyamide is through aromatic dicarboxilic acid and aliphatic diamine or aliphaticdicarboxylic acid and aromatic diamines formation.RI n_D²⁰Below 1.60.

JP-A-62204201 has described a kind of transparent thermoplastic polyamide molding compounds; This compound is to use hexanolactam, cyclohexyl diamines and 2; 2; 4-3-methyl cyclohexanol diamines and terephthalic acid (6/6T/3-6T) preparation, be used to prepare optical lens with high heat distortion temperature and spatial stability advantage.But RI n_D²⁰Well below 1.6.

EP-A-345810 has described the colourless transparent polyamide that is used for lens, is through 2,2 a pair of (3,4 dicarboxylicacid phenyl) hexafluoropropane dianhydrides and the aromatic diamines on a position or 2,4 substituted ditans or propane or RI n_D²⁰The CF on a position greater than 1.6₃, SO₂Form.The density of lens is at 1.33-1.44g/cm³Shortcoming is the formation in 80 ℃ of organic solvents, needs complicated drying process.Lens are under the help of solvent, to use the technology of moulding to prepare.Do not show whether material can thermoplasticity processing in injection-molded machine.

The purpose of this invention is to provide a kind of thermoplastic transparent polyamide molding material, the RI n of above-mentioned copolyamide based on specific copolyamide_D²⁰(greater than 1.6) greater than PMMA, PC, PS and COC, density is low, is no more than the processing temperature of PC and demonstrates the highest hardness and rigidity.

The objective of the invention is to obtain through above-mentioned molding compounds, method and optical lens.Advantage embodiment of the present invention comes from dependent claims.

Surprisingly, the present invention confirms: have high index n aromatic nucleus, above 1.6 based on comprising_D²⁰, less than 1.3g/cm³The transparent polyamide moulding material of copolyamide of diamines of glass transition temp of density, high firmness, low-birefringence property and suitable viscosity and 120-170 ℃ can use such as preparing in the monomer shown in above-mentioned, the autoclave in improved method.The polymeric amide an injectable plastic material advantage that the present invention is used for the thermoplastic lens material is: simple and rational formation.The time that is suitable for preparation lens in the injecting molded method of polymeric amide is the length of several seconds, needs several hrs yet be used to contain the respond lens curing operation of moulding resin.

Through changing the monomeric compound RI n of copolyamide_D²⁰Can change within a large range.Can the material with differing refraction indices can be made up arbitrarily through the compound injection molding methods.Through such as the bonded method such as extruding, join such as additive be used to stablize, painted, enhancing etc.

In the normal pressure autoclave, carry out the preparation of an injectable plastic material of the present invention according to improved method, for example concentrate (condensation).Key is that pressure is no more than 4bar in autoclave.Thermoplastic processing according to common is carried out injection moulding again to moulding material of the present invention.Compare with known material, such as high index n such as PMMA (polymethyl acrylate) or PC (gathering carbonic acid)_D²⁰, hardness, high heat-drawn wire etc. alternative can in this product, can realize.Except being used for the optical feature performance benefit, the molded parts prepared with moulding material of the present invention has good chemical resistance.For example, for optical lens,, need low double refraction for formation and the unsharp image that stops colour circle.

The special benefits of moulding material of the present invention is that it can produce the optical module of load through injection moulding.For example, because outstanding flowability.And the various bound energy of the material that chemistry is compatible use in this method, and its optical property can change.The excellent technique parts that these parts that just allow to constitute anti-polymeric amide constitute.Through using the bonding of polymeric amide to polymeric amide, can be simultaneously with resisting the polymeric amide optical lens to join in the parts of injection moulding.

Another advantage of an injectable plastic material of the present invention is to be lower than 1.3g/cm³Density under high RI n_D²⁰Be more than 1.6.Allow preparation to have light weight but the strong refractor of substantial advantage.

HS through material can obtain another advantage, simplifies treatment step, grinding of aftertreatment and lens for example, and similar with standard injection moulding lens material C R39.High firmness demonstrates good surperficial anti-physical abuse property and can eliminate surperficial purification step, and for example employed hard coat or other protection are scraped.

The necessary advantage of another of polyamide molding material of the present invention is rigidity and the hardness that lens are high.Whereby, handle and the step of scraping can obtain substantial simplification and handles through being used for the polishing agent of Processing Criterion lens CR-39.

Suitable transparent thermoplastic polymeric amide an injectable plastic material of the present invention comprises aromatic dicarboxilic acid.For example isophthalic acid, para Toluic Acid or its mixture; Wherein isophthalic acid constitutes staple.In addition, corresponding ester or other substituted verivate can be used.Crystallization behavior receives the perhaps influence of the selection of asymmetry isomer of different symmetries of naphthalene dicarboxylic acids.The part of aromatic dicarboxilic acid, for example 5mol% can be had the individual aliphatic dicarboxylic acid of 2-12 and replaced.

Summary of the invention

Of the present invention based on copolyamide base transparent thermoplastic polyamide molding material, RI n_D²⁰Surpass 1.59, preferably surpass 1.6, comprise main weight item diamines and the dicarboxylicacid that has aromatic nucleus, it is characterized in that the chain shown in the general formula I is arranged:

[0036]?-{IPS-NH-R₁-NH}_n1-{TPS-NH-R₂-NH}_n2-{CO-R₃-NH}_n3 (I)

[0037]Wherein, n₁=40～100wt%

n₂＝60～0wt％

n₃=0～30wt%, and n₁, n₂, n₃The weight percent summation be 100%, and when n2=n3=0, the transparent thermoplastic polyamide molding material is a polymeric amide;

Have nuclear R₁And R₂Diamines can be identical or different, with respect in the 100mol% diamines at least the diamines of 30mol% by to xylylene or between the xylylene unit constitute, and diamines is by the CH with 2-12₂That the aliphatic chain of unitary linear aliphatic chain or side chain constitutes or diamines is by having single or blended cycloaliphatic nuclear chain constitutes; Comprise in the dicarboxylicacid of 100mol% at least the isophthalic acid of 40mol% (IPS) and; As remainder, can be partly or entirely by the substituted terephthalic acid of naphthalene dicarboxylic acids (TPS).

Above-mentioned nuclear R₃Comprise 5-11 CH₂Unitary chain.

Copolyamide compound shown in the preferred formula II,

MXDI/MXDT/6I/6T (II)

With respect to the diamines of 100mol% and the dicarboxylicacid of 100mol%, each compound composition includes following mol% ratio:

The m-xylylene amine of 30～80mol% (MXD),

The cyclohexyl diamines (6) of 70～20mol%,

The isophthalic acid of 60～80mol% (I) and

The terephthalic acid of 40～20mol% (T).

Transparent thermoplastic polyamide molding material based on copolyamide of the present invention, RI n_D²⁰Surpass 1.59, the copolyamide compound shown in the preferred formula III,

6I/6T/6NDC (III)

The naphthalene dicarboxylic acids of 20～80mol% (NDC) has symmetric or asymmetric the position of substitution or its combination, and particularly 2, the 6-naphthalene dicarboxylic acids,

[0053]The isophthalic acid of 40-20mol% (I),

[0054]40-0mol% terephthalic acid (T) and

The cyclohexanediamine of 100mol% (6).

Between the suitable diamines that the present invention has an aromatic nucleus comprises-xylylene amine and/or right-xylylene amine, can be included in the copolyamide, relatively and the diamines of 100mol% contain 50mol% at least.

The diamines or the aromatic dicarboxilic acid that have aromatic nucleus in the copolyamide in the present invention can be replaced by the have side chain or aromatic diamines non-side chain, a 2-12 carbon atom or 2-12 aliphaticdicarboxylic acid of 5mol%.

Suitable cycloaliphatic diamines or cycloaliphatic dicarboxylicacid comprise such as norcamphyl, cyclohexyl or dicyclohexyl methyl hydride, dicyclohexyl propane, two (methylcyclohexyl) methane, or the skeleton of two (methylcyclohexyl) propane.Described cycloaliphatic diamines or cycloaliphatic dicarboxylicacid can comprise employed cycloaliphatic diamines or the cycloaliphatic dicarboxylicacid that reaches 5mol%.

The suitable dicarboxylicacid with aromatic proton is: isophthalic acid (ISP), its mixture and the combination thereof of terephthalic acid (TPS), the naphthalene dicarboxylic acids with different symmetries or asymmetry isomer, ability conduct acid or ester.

For the polycondensation at copolyamide of the present invention is accelerated, such as H₃PO₂, H₃PO₃, H₃PO₄Phosphorus catalyst join in the aqueous mixture, the total amount of adding is 0.01-0.2wt%.

In order in the course of processing of polymerization and back, to make colour stable, comprise the R of 0.01-0.2wt%₃PO₂, R₃PO₃, R₃PO₄The phosphorus stabilizer agent of type, R is H in the above-mentioned formula, or metals ion or organic linearity or ring-type residue or sterically hindered phenol.

For the length of Quality Initiative, can use excessive diamines or dicarboxylicacid, or in simple function group amine or simple function group acid polymerization gone into; As the acid of simple function group acid particularly TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M., acetate, propionic acid, as the amine of simple function group amine particularly hexylamine and/or cyclo-hexylamine.The control agent that preferably has the stablizer function, for example many alternate piperidyl and tert-butyl-phenyl functional group.

Copolyamide of the present invention between 5%-relative viscosity that cresols is measured is 1.33-1.65.

Daiamid composition of the present invention-that is to say moulding material-ability other for additive well-known to those having ordinary skill in the art; Especially, moulding material of the present invention comprise additive such as the filtering UV absorption agent of UV that will be below 400nm, be used for to lens staining dyestuff, or according to the thermotropism of temperature or wavelength shift color or hot color admixture, be used to improve impact strength etc. refraction grafted nuclear-covering (isorefractive grafted core-cladding) polymkeric substance or lubricant, or other processing auxiliary agent, or group like perhaps spherical or anti-albefaction (anti-bloom) reagent of glass optical fiber.

Injection moulding property material of the present invention prepares in autoclave through known concentrating means, and its distinct feature is that any procedure of processing does not all surpass BP 10bar, perhaps preferred 4bar.Under elevated pressures, these diamines that have aromatic nucleus form side chain easily, thereby have quickened melt viscosity, for example at 260 ℃, and make and from reactor drum, can not pour out.

Employed chemical combination method representation adds the appropriate method of needed additive in extruding; UV absorption agent for example, be used for the UV below 400nm filter out, be used for to lens carry out painted dyestuff, or change outward appearance based on temperature effect, or according to temperature or get into color admixture that light wavelength changes color, be used for impact strength etc. the polymkeric substance of refraction bonding ring (graftedcore-cladding polymer).

Any thermoplasticity that is used for especially all is suitable for the particle that from an injectable plastic material, obtains is injection molded into optical lens again in any known method of porous instrument, for example the lens blank.

Through have polarization characteristic or have such as the UV absorption agent that can filter the UV below the 400nm, be used for to lens carry out painted dyestuff, or change outward appearance based on temperature effect, or according to temperature or the film or the other an injectable plastic material articles injection-moulded of the present invention that get into the back injection moulding of the color admixture that light wavelength changes color can prepare compound lens.And the compound lens that the back injection of the protective membrane through using lens material obtains can influence chemical resistant properties, anti-mechanical pressure property and friction resistant abradability.

The suitable applications of high refraction moulding material of the present invention comprises the lens that are used for glasses, photographic camera, field glass, microscope, transilluminator, form and decorate mirror.

To the finishing of the moulding bodies that will prepare, can use known method, for example be coated with firmly, soft being coated with scrape or the UV protection is scraped, evaporated coating, plasma treatment and layers of polymer through carbon or atoms metal.

These moulding materials of the present invention can be used for other amorphous or semi-crystalline polymeric amide and modify with commonly used toughener, nanoparticle, impact strength properties-correcting agent, fire retardant, tenderizer and lubricant as mixing cpd.

Following embodiment 3-9 is used for explaining, and embodiment 1 and 2 handles preparation and the performance of known product TR55 and

.

Reference implementation example 1

(VB1)

With 13; 4kg laurine lactan, 10.7kg cycloaliphatic diamines (Laromin 260BASF), 190g TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M., be suspended in the 40kg water of pressure autoclave of 130L; Heating is 2 hours under 260 ℃ of temperature; Continue down to react 3 hours with 20bar at 290 ℃ in the pressure stage at about 20bar. through the released vapour restriction pressure simultaneously, slowly pressure is reduced to 1bar and exitted about more than 3 hours in the expansion stages then.After reaching needed whisking appliance torque, through boring (borehole) the turned letter mixture of about 5mm.Connect the polymer strands that occurs through a water-bath chamber, particle is cut in cooling then.Then, in roller dryer 90 ℃ dry 12 hours down.1.55 glass polymeric amide colourless, glass transition temp appears is measuring in 165 ℃ and between the 5%-cresol liquor relative viscosity and be.

On the injection-molded machine of Arburg, the molded parts from dried particles is made.Temperature of fusion is arranged on 270-290 ℃, and molding temperature is arranged on 60-80 ℃.The performance of molded parts is summarised in the table 1.

Reference implementation example 2

With 14; 4kg cyclohexanediamine, the different phthalic acid of 13.6kg, 6.8kg terephthalic acid, 125g acetate, be suspended in the 40kg water of pressure autoclave of 130L; Under 280 ℃ of temperature the heating 2 hours, in the pressure stage, through the released vapour restriction pressure at about 20bar; In the ensuing expansion stages, continue to stir down and slowly pressure is reduced to 1bar and exitted about more than 3 hours at 280 ℃.After reaching needed whisking appliance torque, through boring (borehole) the turned letter mixture of about 5mm.Connect the polymer strands that occurs through a water-bath chamber, particle is cut in cooling then.Then, in roller dryer 90 ℃ dry 12 hours down.1.45 glass polymeric amide colourless, glass transition temp appears is measuring in 130 ℃ and between the 5%-cresol liquor relative viscosity and be.Polymer properties is summarised in the table 1.

On the injection-molded machine of Arburg, the molded parts from dried particles is made.Temperature of fusion is arranged on 260-280 ℃, and molding temperature is arranged on 50-80 ℃.The performance of molded parts is summarised in the table 1.

Embodiment 3 and 8 (according to the present invention)

With 6.44kg cyclohexanediamine, 8.75kg m-xylylene amine, 13.13kg isophthalic acid, 6.56kg terephthalic acid, 125g acetate, be suspended in the 40kg water of pressure autoclave of 130L; Heating is 2 hours under 140 ℃ of temperature; With commonly used process mutually this; Pressure is arranged on 3.5bar, and skipping the pressure stage directly expands.Be heated to 260 ℃ with expansion simultaneously, so that the pressure in autoclave is always below 4bar.Then, continue stirring and slowly pressure is reduced to 1bar and exitted about more than 3 hours.After reaching needed whisking appliance torque, through boring (borehole) the turned letter mixture of about 5mm.Connect the polymer strands that occurs through a water-bath chamber, particle is cut in cooling then.Then, nitrogen and 100 ℃ dry 12 hours down in roller dryer.Colourless, glass transition temp occurring and be measuring relative viscosity in 139-141 ℃ and between the 5%-cresol liquor is the glass polymeric amide of 1.42-1.45.Polymer properties is summarised in the table 1.

On the injection-molded machine of Arburg, the molded parts from dried particles is made.Temperature of fusion is arranged on 250-275 ℃, and molding temperature is arranged on 30-50 ℃.The performance of molded parts is summarised in the table 1.

Embodiment 4,5,6 and 7 (according to the present invention)

In the quantity that increases gradually with the listed m-xylylene amine of table 1, among the embodiment 4 similar, in 5,6 and 7 with embodiment 3, the preparation polymeric amide.

Embodiment 9 (according to the present invention)

With 14.1 cyclohexanediamine, 3.5 naphthalene dicarboxylic acids 2; 6 [sic.p.17], 17.2kg isophthalic acid, 230g acetate, be suspended in the 40kg water of pressure autoclave of 130L; Heating is 2 hours under 260 ℃ of temperature, is about 4bar. to the maximum through the released vapour restriction pressure simultaneously and continues to stir down and slowly pressure is reduced to 1bar and exitted about more than 3 hours at 260 ℃.After reaching needed whisking appliance torque, through boring (borehole) the turned letter mixture of about 5mm.Connect the polymer strands that occurs through a water-bath chamber, particle is cut in cooling then.Then, in roller dryer 90 ℃ dry 12 hours down.1.48 glass polymeric amide colourless, glass transition temp appears is measuring in 132 ℃ and between the 5%-cresol liquor relative viscosity and be.

TR55:

TR55, (EMS chemistry)

G21:

G21 (FMS chemistry)

R.V.0.5% meta-cresol: the relative viscosity that in 0.5% meta-cresol, measures

MVI=melt viscosity index

The mensuration of performance

The characteristic of " COND " water that uses is on the specimen that has reached requirement, to measure.Training is carried out according to ISO1110.All residue performances are all measured on the exsiccant specimen.

The mensuration of hot data is carried out on particle (drying: 120 ℃/24 hours), and device is Perkin Elmer DSC, and heating rate is 20 ℃/min, and rate of cooling is 5 ℃/min.

Melt temperature is tested according to ISO3146-C.Crystallized temperature, crystallization enthalpy and crystallization speed are (5 ℃/min) measure of refrigeration cycle.In order to measure glass transition temp Tg, sample is heated to Tg+20 ℃ to be measured in second thermal cycling with extinguishing then (20 ℃/min).

Under 20 ℃ and in the cutout of molded parts, use pycnometric determination density.

Use Gottfert, measure MVI according to DIN53735/ISO1133.Be 275 ℃ heat-up time and heated 4 minutes down that mensuration is carried out under 5kg.

It is through carrying out according to the tension test on the standard testing sample of ISO527 that the mechanical property of the prolongation when E-module, tensile strength, fracture is measured.

Impact strength, (SZ) and indentation impact strength (KSZ) are according to ISO 179eU and ISO179eA, measure under 23 ℃ through Charpy.

Use Perkin Elmer UV device, in the 200-800nm scope, on the colored disk of 50 * 30 * 3mm, measure optical transmission.Transmission numerical value is that the wavelength at 540nm (3mm) provides.

Use daylight, on look look disk, use and measure 50 * 30 * 3mm, measure refractive index at the Abbe refractometer.Refractive index is n_D²⁰Numerical value.

According to ISO868, at room temperature, to meeting the requirements of sample determination hardness Shao Er D.

Claims

1. transparent thermoplastic polyamide molding material based on copolyamide, RI n_D²⁰Surpass 1.59, staple is diamines and the dicarboxylicacid that has aromatic proton, it is characterized in that the chain shown in the general formula I is arranged:

-{IPS-NH-R₁-NH}_n1-{TPS-NH-R₂-NH}_n2-{CO-R₃-NH}_n3 (I)

Wherein, n₁=40～100wt%

n₂＝60～0wt％

n₃=0～30wt%, and n₁, n₂, n₃Part by weight (wt%) summation be 100%, IPS is an isophthalic acid, TPS is a terephthalic acid;

Have nuclear R₁And R₂Diamines can be identical or different, with respect in the 100mol% diamines at least the diamines of 30mol% be by to xylylene or between the xylylene unit constitute, and diamines is by the CH with 2-12₂The aliphatic chain of unitary linear aliphatic chain or side chain constitutes or diamines is by having single or blended cycloaliphatic nuclear chain constitutes; Comprise in the dicarboxylicacid of 100mol% 40mol% at least isophthalic acid and; As remainder; Can be partly or entirely by the substituted terephthalic acid of naphthalene dicarboxylic acids, above-mentioned nuclear R₃Comprise 5-11 CH₂Unitary chain.

2. transparent thermoplastic polyamide molding material as claimed in claim 1, RI n_D²⁰Surpass 1.59, it is characterized in that copolyamide has the compound shown in the general formula (II):

MXDI/MXDT/6I/6T (II)

For the dicarboxylicacid of the diamines of 100mol% and 100mol%, each compound composition includes following mol% ratio:

The m-xylylene amine of 30～80mol% (MXD),

The cyclohexyl diamines (6) of 70～20mol%,

The isophthalic acid of 60～80mol% (I) and

The terephthalic acid of 40～20mol% (T).

3. like any described transparent thermoplastic polyamide molding material of claim 1-2, it is characterized in that copolyamide comprises the diamines that has aromatic nucleus based on the 50mol% at least of 100mol% diamines.

4. transparent thermoplastic polyamide molding material as claimed in claim 3 is characterized in that, copolyamide comprises the diamines that has aromatic nucleus based on the 50mol% at least of 100mol% diamines, is m-xylylene amine, to xylylene amine.

5. transparent thermoplastic polyamide molding material as claimed in claim 4 is characterized in that, up to the diamines of 5mol% and/or have aromatic nucleus dicarboxylicacid can by side chain or not branched, have a 2-12 (CH₂) unitary aliphatie diamine or have 2-12 (CH₂) unitary side chain or be not that the aliphatic dicarboxylic acid of side chain replaces.

6. transparent thermoplastic polyamide molding material as claimed in claim 5; It is characterized in that having up to cycloaliphatic diamines or cycloaliphatic dicarboxylicacid 5mol%, that have in the skeleton that is selected from norcamphyl, cyclohexyl or dicyclohexyl methyl hydride, dicyclohexyl propane, two (methylcyclohexyl) methane, two (methylcyclohexyl) propane to be included in the chain of copolyamide.

7. transparent thermoplastic polyamide molding material as claimed in claim 6 is characterized in that, in order in the course of processing of polymerization and back, to make colour stable, comprises the R of 0.01-0.2wt%₃PO₂, R₃PO₃, R₃PO₄The phosphorus stabilizer agent of type and R is H, or metals ion or organic linearity or ring-type residue or sterically hindered phenol.

8. transparent thermoplastic polyamide molding material as claimed in claim 7 is characterized in that, for the length of Quality Initiative, can use excessive diamines or dicarboxylicacid, or in simple function group amine or simple function group acid polymerization gone into.

9. transparent thermoplastic polyamide molding material as claimed in claim 8 is characterized in that, for the length of Quality Initiative, uses the control agent that has the stablizer function.

10. transparent thermoplastic polyamide molding material as claimed in claim 8 is characterized in that, uses polysubstituted piperidyl and tert-butyl-phenyl functional group.

11. transparent thermoplastic polyamide molding material as claimed in claim 8 is characterized in that, simple function group amine is fat or cycloaliphatic amine; And simple function group acid is fat or aromatic acid.

12. transparent thermoplastic polyamide molding material as claimed in claim 11 is characterized in that, simple function group amine is hexylamine and/or cyclo-hexylamine.

13. transparent thermoplastic polyamide molding material as claimed in claim 11 is characterized in that, simple function group acid is TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M., acetate, propionic acid.

14. transparent thermoplastic polyamide molding material as claimed in claim 13 is characterized in that, the relative viscosity (r.V.) of the copolyamide of mensuration 5% is 1.33-1.65 in meta-cresol.

15. transparent thermoplastic polyamide molding material as claimed in claim 14 is characterized in that, in order to promote reaction, in polycondensation, will be selected from H₃PO₂, H₃PO₃, H₃PO₄In phosphorus catalyst join in the aqueous mixture, the total amount of adding is 0.01-0.2wt%.

16. the preparation method of a moulding bodies; Be suitable for one or more the desired moulding material among the claim 1-15; It is characterized in that; Use the method for known manufacturing moulding material, with injection-molded, the particle that from molding compounds, prepares is reinvented into optical lens or lens blank.

17. the preparation method of moulding bodies as claimed in claim 16 is characterized in that, uses the method for known manufacturing moulding material, in the porous utensil, the particle that from molding compounds, prepares is reinvented into optical lens or lens blank.

18. the preparation method of moulding bodies as claimed in claim 16; It is characterized in that; Film and other molded parts; Be that (back-injection) injected in the back; Above-mentioned parts have polarization characteristic, or have the absorption agent that can filter following the UV of 400nm, perhaps have the dyestuff that is used for the imbue mirror, or have and can change outward appearance, or have according to temperature and perhaps get into the color admixture that light wavelength changes color based on temperature effect, wherein protective membrane after be injected at and obtained improved anti-chemical, improved loading capacity, improved friction resistant and polishing machine on the molded parts.

19. preparation method like any described moulding bodies of claim 16-18; It is characterized in that, be the modification that has stiff dough, soft or UV protection glossy surface, evaporation coating, plasma treatment, the layers of polymer with carbon or atoms metal with finishing.

20. an optical lens that is used for glasses is characterized in that, these lens are through desired invention moulding material of claim 1-15 and the described method preparation of claim 16-19.

21. optical lens; Be applicable to photographic camera, field glass, microscope, electron optics test and test set, optical filter, headlight lens, lamp lens, projector and video projection machine, viewing window or amount liquid glass; It is characterized in that these lens are through desired invention moulding material of claim 1-15 and the described method preparation of claim 16-19.

22. the application of a moulding material; Use any described polyamide molding material of claim 1-15 to prepare mixture or alloy; It is characterized in that; The polymeric amide of unbodied or hemihedral crystal build being used as mixture or alloy, add additive commonly used, is toughener, nanoparticle, impact strength properties-correcting agent, fire retardant, tenderizer, stablizer, lubricant.

23. transparent thermoplastic polyamide molding material as claimed in claim 1 is characterized in that RI n_D²⁰Surpass 1.6.